Fuel element for a pressurized water reactor and method for producing cladding tubes

ABSTRACT

A fuel element for a pressurized water reactor is described. The fuel element contains a laterally open skeleton having control-rod guide tubes each with a first end and a second end, spacers fastened to the control-rod guide tubes, a fuel element head disposed at the first end of the control-rod guide tubes, and a fuel element foot disposed at the second end of the control-rod guide tubes. Gastight cladding tubes are inserted into the skeleton and each is filled with a column of fuel pellets. At least some of the gastight cladding tubes have a multilayer wall. The multilayer wall is formed of a mechanically stable matrix containing a first zirconium alloy disposed in a middle of the multiplayer wall; and a thinner protective layer of a second zirconium alloy alloyed to a lesser extent than the first zirconium alloy. The thinner protective layer is bound metallurgically to the matrix and is disposed on an inside of the matrix facing the fuel pellets.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of copending InternationalApplication No. PCT/EP00/02681, filed Mar. 27, 2000, which designatedthe United States.

BACKGROUND OF THE INVENTION

Field of the Invention

The invention relates to a fuel element for a pressurized water reactor,with a laterally open skeleton containing control-rod guide tubes, towhich are fastened a plurality of spacers and also a fuel element headand a fuel element foot. Gastight multilayer cladding tubes are insertedinto the skeleton and in each case surround a column of fuel pellets.The invention relates, furthermore, to a method for producing thecladding tubes.

FIG. 1 illustrates a fuel element of this type, with a head 1, a foot 2and spacers 3 and 4 that are fastened to guide tubes 5, thus producing alaterally open skeleton, into which fuel rods 6 are inserted. Duringoperation, cooling water flows from the bottom upward through the fuelelement and can also enter adjacent fuel elements laterally from theinterspaces between the fuel rods. It can also be seen from FIG. 1 thatadditional mixing grids 7, which serve as carriers for flow guideblades, may be provided between the spacers 4 in an upper part of thefuel element. Such flow guide blades are advantageously likewiseprovided in the upper part of the fuel element, at least on a top sideof the spacers 4, in order to achieve a turbulent mixing of the coolingwater and a better flow onto the fuel rods 6.

Corresponding blades are described, for example, in Published,Non-Prosecuted German Patent Application DE 15 64 697 A and arereproduced in FIG. 2. It is also possible, however, to have otherspacers (for example, formed of sleeves welded to one another) and othergeometries of flow guide blades 8, while a different number of mixingvanes may also be provided in the interspaces between adjacent fuel rods6.

In the pressurized water reactor, only a small fraction (normally atmost 5%) of the liquid cooling water is evaporated on the outer surfacesof the fuel rods, on the contrary the heat generated in the fuel bynuclear fission is discharged essentially in that water having acorresponding temperature and maintained under high pressure istransported away by convection. In contrast, a boiling water reactoroperates with lower pressure and lower temperatures, the heat from thefuel rods being transported away, at least in the upper part of the fuelelement, essentially by isothermal evaporation in a two-phase mixture.In this case, it is necessary to channel the steam that occurs. The fuelelements are therefore surrounded laterally by fuel element boxes.

The techniques of the boiling water reactor and of the pressurized waterreactor have developed in different directions. For the purpose of plantprotection and for similar reasons, the pressurized water has admixedwith it, for example, lithium hydroxide and similar additives whichcannot be used in boiling water and lead to a different water chemistry(for example, a different oxygen concentration). The size and number offuel rods in the fuel elements and the configuration of control elementsin the reactor core are also different. The differences in thetemperature and pressure of the cooling water also lead to differentloads on the cladding tubes and to a different behavior of the fuel, inparticular to different time constants of the reactor core when thelatter is considered as a self-contained control system with feedback.

The result of this different control behavior is that the power outputof pressurized water reactors is changed only very slowly, that is tosay the pressurized water reactor is operated almost virtually in thesteady state and is suitable particularly for covering basic loads. Forcovering peak loads of the consumer connected to the reactor, boilingwater reactors, the power output of which is run up, for example,substantially more quickly and in a ramp-like manner, are more suitable.The result of this is that the cladding tubes, which are already exposedon their outer surface, according to the different water chemistry andoperating temperatures, to different chemical loads (for example,nodular corrosion in the boiling water reactor or uniform corrosion inthe pressurized water reactor) and have to withstand different operatingpressures, are also subjected to different loads on the inside.

The outcome of this has been that the cladding tubes of boiling waterreactors are formed, as a rule, of a different alloy (to be precise,zircaloy-2) from the cladding tubes of pressurized water reactors forwhich zircaloy-4 was developed. A zirconium alloy with 2.5% niobium,which is also used in Russian light-water cooled reactors, is also knownfor the pressure tubes of high-temperature reactors.

Table 1 indicates the standardized composition of industrially purezirconium for the nuclear industry (so-called “zirconium sponge”),zircaloy-2 (“zry-2”), zircaloy-4 (“zry-4”) and zirconium niobium(“Zr/Nb”), oxygen being considered as an impurity acceptable in smallquantities, even when, because of its hardening effect on zirconium, itis often desirable and is therefore added.

If use is made of a higher enrichment of the fuel pellets withfissionable isotopes of uranium and/or plutonium and therefore of agreater useful energy content (so-called “burn-up”) of the fuel, thenthe fuel elements can remain in the core for longer, should theircladding tubes be capable of meeting the corresponding requirements dueto the longer service life. Therefore, in pressurized water fuelelements, the outer surfaces of the cladding tubes must be particularlyresistant to the uniform corrosion occurring in the pressurized waterand should not be pressed onto the fuel by the increased pressure, evenin the event of relatively long service lives, in such a way that theythereby experience damage. In the development of cladding tubes thatmeet the increased requirements of a longer service life in thepressurized water reactor, it is therefore necessary to pay particularattention to the mechanical stability of the entire tube and to theresistance of the outer surface to uniform corrosion.

These conditions are fulfilled satisfactorily by single-layer claddingtubes, such as are described in European Patent EP 0 498 259 B and, ingeneral, consist of zirconium with 0.8 . . . 1.7% Sn, 0.07 . . . 0.5%Fe, 0.05 . . . 0.35% Cr, 0.07 . . . 0.2% O, up to about 0.015% Si and upto a maximum of 0.1% Ni. In this context, it has proved particularlyimportant that the metals, Fe, Cr and Ni, which are virtually insolublein zirconium and are precipitated (so-called “secondary precipitations”)as intermetallic compounds (“secondary phases”), have an averageparticle size of about 0.1 to 0.3μ. The particle size is set by thethermal treatment to which the alloy is subjected after it has firstbeen brought to a temperature at which the precipitations are dissolved(so-called “solution annealing”) and has then been rapidly cooled(so-called “quenching”). The resulting size and distribution of thesecondary precipitations can be calculated by a “particle growthparameter” and in manufacturing practice are set by a cumulative“standardized annealing duration” AA=Σt _(i)·exp(−Q/T),in which T is the temperature in Kelvin during a manufacturing step i,t_(i) is the duration of the manufacturing step and Q corresponds to anactivating energy, and the value Q=40,000 Kelvin may be adopted.

FIG. 3 shows the daily growth of the uniform oxidation layer on thesurface of a cladding tube formed of zircaloy-4 in a pressurized waterreactor at operating temperatures of about 300° C. as a function of thestandardized annealing duration A which was used in the production ofthe cladding tube. In general, for pressurized water reactors,standardized annealing durations of between 2·10⁻¹⁸ and 50·10⁻¹⁸ hoursare considered favorable for zircaloy-like alloys of this type, such asare described in European Patent EP 0 498 259 B (Garzarolli et al. in“Zirconium in the Nuclear Industry: Eighth International Symposium”,Philadelphia 1989 (ASTM Special Technical Publication 1023), pages 202to 212). However, such a high annealing duration conflicts with theefforts of a person skilled in the art, by a pilgrim-step method withcold formings, to break down the alloy grain, which likewise ripens intolarge grains at high temperatures, into small grains by cold formings,in order to increase the mechanical stability of the cladding tube,since a fine grain leads to high stability along with high ductility.Consequently, according to the patent specification mentioned, the highstandardized annealing duration is achieved by the quenched materialfirst being forged, still at a high temperature, before it is extrudedto form a tube blank and is then cold-formed in subsequent pilgrim stepswith moderate intermediate annealings.

Another way is to have a composite tube that, as a so-called “duplex”,formed of a relatively thick matrix layer with a thin outer protectivelayer formed of another zirconium alloy. The matrix ensures thenecessary mechanical stability, while the outer protective layer isresistant to the uniform corrosion posing a threat in the pressurizedwater reactor. Such a duplex is described for the first time in EuropeanPatent EP 0 212 351 B, where 0.1 to 1% V and up to 1% Fe is used asalloying additives for the outer protective layer. European Patent EP 0301 295 B describes a duplex, in which the outer alloy contains 0.2 to3% Nb and/or a total content of Fe, Cr, Ni and Sn of between 0.4 and 1%(remainder: in each case zirconium of industrial purity). It is knownfrom European Patent EP 0 630 514 B that an outer layer of this type fora zircaloy matrix may also contain a larger total content of Fe, Cr, Ni,Sn, insofar as specific restrictions are maintained for the individualalloying additives, in particular the tin content is below the tincontent of the zircaloy. The cladding tubes mentioned have provedappropriate, even under the operating conditions of the pressurizedwater reactor, and make it possible to achieve the desired long servicelives.

The graph of FIG. 3 would be entirely different in the case of a boilingwater reactor. There, because of the lower operating temperatures,virtually no uniform corrosion occurs, but oxide pustules are formed.Here, high secondary precipitations cannot act as any of the pustulesthat, however, are avoided when the material of the secondary phases isfinely distributed and has undergone only a particularly lowstandardized annealing duration. Often, however, cladding tubes ofboiling water fuel rods exhibited corrosion damage that emanated frominside the tubes and was attributed to stress crack corrosion. Suchdamage was minimized by a composite tube, in which a matrix of zircaloyhad on the inside a protective layer of industrially pure zirconium,that is to say a soft material, but one susceptible to corrosion. Inthis case, however, the susceptibility of pure zirconium to corrosion isa disadvantage, since the situation is unavoidable where, in rareinstances, due to slight damage in the tube, water from the boilingwater reactor enters the cladding tube interior and then triggerscorrosion leading to extensive cracks by which the water of the reactormay be contaminated to a substantially greater extent than by amultiplicity of fuel rods with locally limited damage. Instead of aprotective layer of pure zirconium, therefore, a protective layer isoften used, in which the zirconium contains up to 1% of another alloyingadditive. Thus, European Patent EP 0 726 966 B describes a cladding tubewith a thick matrix layer of zircaloy, in which the secondaryprecipitations have a particle size of between about 0.03 and 0.1μ, anda lining of zirconium with 0.2 to 0.8% iron is bonded metallurgically tothe inside.

The composite tube is particularly advantageous in the boiling waterreactor, because, due to the small size of the secondary precipitationson the outer surface, a particularly low A-value becomes necessary,which, in the case of the appropriate alloying of the protective layeron the inside of the cladding tube, likewise brings about only a slightgrowth of secondary precipitations and grain, so that the inside is bothprotected more effectively against corrosion and remains soft because itis not subject to any excessive dispersion hardening as a result of Fesecondary precipitations.

However, a cladding tube of this type, configured for boiling waterconditions, is entirely unsuitable for pressurized water applications,since the small size of the secondary precipitations on the outersurface would accelerate the uniform corrosion and necessitate anexchange of the cladding tube even after short service lives. On theother hand, the inner lining is not necessary, even under the operatingconditions of the pressurized water reactor which have existed hitherto,since, up to now, no damage emanating from the inner surface (stresscrack corrosion) has been observed. Moreover, the power output of thepressurized water reactors is not changed rapidly in the ramp-likemanner, as is customary in boiling water reactors. Instead, the controlconditions of the pressurized water reactor make it necessary, in anycase, for the power output to be changed only slowly, there beingpredetermined for the control a rate of change which also takes accountof the fact that the cladding tubes are not to be subjected toinadmissible stress.

In the case of a higher enrichment of the fuel and longer service lives,even the behavior of the fuel itself must be taken into consideration.Since a multiplicity of gaseous fission products occur duringdecomposition, the fuel swells and thereby experiences an enlargement ofvolume which leads to a widening of the cladding tube, especially sincethe latter, in the course of time, particularly under the higherpressures of the pressurized water reactor, is compressed and creepsonto the fuel. When the fuel, which is in contact with the inside of thecladding tube even at a low reactor power output, is quickly heated as aresult of a rapid increase in power output customary in the boilingwater reactor, however, the thermal expansion of the fuel constitutes anadditional load on the cladding tube. In configuration terms, the loadscan be taken into account in as much as a gas collecting space isprovided at least in the upper end of the fuel rods, a gap is left freebetween the cladding tubes and the fuel pellets and the fuel element isefficiently and quickly cooled, for example by the initially mentionedflow guide blades on the spacers and, if appropriate, additionallyintroduced intermediate grids. The load has hitherto been unimportant inthe control of the power output of pressurized water reactors, since, inany case, in control terms a restricted rate of change of the poweroutput seems permissible.

SUMMARY OF THE INVENTION

It is accordingly an object of the invention to provide a fuel elementfor a pressurized water reactor and a method for producing claddingtubes that overcome the above-mentioned disadvantages of the prior artdevices and methods of this general type, which, on the one hand, canremain in the reactor for a sufficiently long time and, on the otherhand, allows a more flexible operation of the pressurized water reactor,in particular use of the pressurized water reactor for covering peaks indemand of the consumer or power supply network connected to the reactor.In particular, the object, at the same time, is to produce a claddingtube suitable for the novel fuel element.

With the foregoing and other objects in view there is provided, inaccordance with the invention, a fuel element for a pressurized waterreactor. The fuel element contains a laterally open skeleton havingcontrol-rod guide tubes each with a first end and a second end, spacersfastened to the control-rod guide tubes, a fuel element head disposed atthe first end of the control-rod guide tubes, and a fuel element footdisposed at the second end of the control-rod guide tubes. Gastightcladding tubes are inserted into the skeleton and each is filled with acolumn of fuel pellets. At least some of the gastight cladding tubeshave a multilayer wall. The multilayer wall is formed of a mechanicallystable matrix containing a first zirconium alloy disposed in a middle ofthe multiplayer wall; and a thinner protective layer of a secondzirconium alloy alloyed to a lesser extent than the first zirconiumalloy. The thinner protective layer is bound metallurgically to thematrix and is disposed on an inside of the matrix facing the fuelpellets.

The invention proceeds, in this case, from the knowledge that thecontrol restrictions in the control of the power output make it possibleper se to have greater rates of change in the power output of apressurized water reactor than has been conventional hitherto. Flexibleoperation would therefore be possible if the fuel element were also towithstand the loads occurring during rapid load changes.

To achieve the object, the invention provides the fuel element with alaterally open skeleton containing the control-rod guide tubes, to whichare fastened the spacers, the fuel element head and the fuel elementfoot. Inserted into the skeleton are the cladding tubes which in eachcase surround a column of fuel pellets in a gastight manner, at leastsome cladding tubes each having a multilayer wall. In the middle of thewall is located, according to the invention, a mechanically stablematrix of a first zirconium alloy, alloyed to a greater extent, to whicha thinner protective layer of a second zirconium alloy alloyed to alesser extent is bound metallurgically. The protective layer is in thiscase located on the matrix inside facing the fuel pellets. Preferably,the two zirconium alloys have precipitations of secondary phases that,by thermal treatments with different standardized annealing durations,are ripened to a different average size.

The invention is in this case based on the fact that the configurationof the fuel element satisfies all hydraulic and cooling requirements ofrelatively long operation under full load or part load, particularlywhen at least the spacers in an upper part of the fuel element carry, ontheir side facing away from the flow of pressurized water, flow guideblades for intermixing the pressurized water. The configuration of thefuel rods can also satisfy these requirements, particularly when thecladding tubes are filled with a gas of increased pressure and have agas collecting space (“plenum”) at least at the upper end and thepellets are introduced with an annular gap in relation to the innersurface of the cladding tube.

Moreover, the invention also takes account of the fact that a matrix, inparticular when it has the features described in European Patent EP 0498 259 B, is already sufficiently corrosion-resistant for relativelylong operation under full load. If appropriate, a further protectivelayer, such as is described, for example, in European Patents EP 0 212351 B, EP 0 301 295 B or EP 0 630 514 B mentioned, may also be bondedmetallurgically around the matrix on the outside of the cladding tube.

A matrix of this type, formed of a zircaloy-like zirconium alloy (1 to1.8% by weight Sn; 0.2 to 0.6% by weight Fe; up to 0.3% by weight Cr;remainder: industrially pure zirconium, if appropriate with an oxygencontent of up to 2.0%), best displays the desired properties when it istreated with a standardized annealing duration A of between 2 and80·10⁻¹⁸ hours.

Another preferred possibility for a matrix having the desired propertiesis a zirconium alloy with 0.8 to 2.8% Nb (if appropriate, up to 2.7% offurther additives, remainder: zirconium of industrial purity, including,if appropriate, an oxygen content of up to 2.0%). Preferably, in thiscase, the quantity of further additives is below the quantity of theniobium. However, such a niobium-containing zirconium alloy displays themost favorable properties when it is subjected to a substantially lowerstandardized annealing duration, in particular A lower than 0.5·10⁻¹⁸ h.

Admittedly, the mechanical stability of the alloys is not so high thatthey ensure the annular gap for a relatively long time and could preventthe cladding tube from creeping down onto the fuel. The alloys overcomethe fact that the cladding tube is widened again due to the growth involume of the fuel after relatively long service lives. The alloys alsowithstand load changes during which the power output falls considerablybelow the maximum value for only a short time and is soon raised againto the maximum value.

To control the power output, however, the rate of change must be adaptedto the most unfavorable case. This occurs when, during the operation ofthe reactor, a plurality of load changes have already taken place andthen only part-load operation takes place for a relatively long time, inwhich the fuel contracts thermally and a renewed creeping of thecladding tube consequently occurs. There is then the threat of suddenloads when the reactor is quickly run up again and the fuel expandsthermally again. This, in actual fact, requires a particularly highductility of the cladding tube, which, however, would itself beconducive to undesirably rapid creeping.

Moreover, when, by the control elements being moved out, the reactor isrun up from a state in which it was operated only under part load, withcontrol elements inserted partially into the reactor core, the fuelpellets adjacent to the control elements which are moving pastexperiencing a sudden thermal load, since they were previously protectedby the control elements from the high neutron flux to which they arethen suddenly exposed. The pellets, which were initially intactaccording to FIG. 4, therefore shatter and experience a structuralchange evident from FIG. 5. In this case, individual fragments of ashattered pellet may be displaced and press locally against the insideof the cladding tube. It must therefore be assumed that, after a lengthyperiod under part load, close contact occurs at least locally betweenthe fuel rod and the fuel (“deconditioning”) and then, in the case of asudden thermal change in volume of the fuel, generates considerablestresses in the cladding tube.

If the cladding tube is formed completely of the alloys mentionedhitherto, only slow increases in power output would thereforenevertheless be possible. According to the invention, however, thestresses are absorbed by the protective layer bound metallurgically tothe inside of the matrix and formed of the zirconium alloyed to a lesserextent, the protective layer formed preferably of zirconium ofindustrial purity which is alloyed with 0.2 to 0.8% by weight of iron.As a rule, the second zirconium alloy contains more than 0.3% by weight,preferably at least 0.35% of iron. The preferred maximum value is around0.5 or, in any event, is below 0.6%.

However, the alloy displays the most favorable properties when theprecipitations of the secondary phases have an average size whichcorresponds to a standardized annealing duration of about 0.1 . . .3·10⁻¹⁸ h.

Such small secondary precipitations of a ZrSe alloy on the inside of thecladding tube are known from the initially mentioned European Patent EP0 726 966 B and can be manufactured from a composite tube blank producedby the coextrusion of tubes inserted one into the other, but the resultof the further processing of the blank is that, after quenching, the twolayers acquire either a high A-value, this being detrimental to theaction of the protective layer, or a low A-value, that is to say theoutside also has correspondingly fine secondary precipitations, whichconforms to the requirements of a boiling water reactor, but is harmfulto a pressurized water reactor.

However, different precipitation sizes on the inner surface and theouter surface of a cladding tube can be produced by a method that isknown as “partial quenching”. In this, in the case of a cladding tubewhich already possesses relatively large secondary precipitations due torelatively long annealing durations, the inside is maintained at a lowtemperature by a coolant stream, while the outside is increased briefly(for example, inductively) to solution temperature. During cooling, afine dispersion of precipitations occurs on the outside, that is to say,ultimately, a “metallurgic gradient” with respect to the precipitationsin the cladding tube is generated. However, the result of the“metallurgic gradient” is precisely that there are substantially finersecondary precipitations on the outside than on the inside, that is tosay precisely the distribution likewise suitable only for boiling water,if both layers are formed of a niobium-free ZrFe alloy.

The “partial quenching” is complicated, but is possible, at leasttheoretically, in the case where the matrix is formed from a ZrNb alloy.

However, such a cladding tube with a matrix of ZrNb, which is bondedmetallurgically to the inside of the cladding tube by a protective layerof ZrFe, can also be produced by the two zirconium alloys first beingthermally treated independently of one another, in each case solutionannealing, with subsequent different standardized annealing durations A,being carried out. From the first zirconium alloy and at least thesecond zirconium alloy, a multilayer composite tube is then produced,the wall of which contains in the middle a thick layer of the firstzirconium alloy as the matrix, a protective layer of the second alloybeing bonded metallurgically to the inside of said wall. The compositetube is then processed further into the finished cladding tube, in sucha way that the two layers are in this case subjected to virtually thesame thermal conditions, without solution annealing.

In this case, the second zirconium alloy is treated, up to thecompletion of the cladding tube, with a standardized annealing durationwhich differs by at least 80% from the standardized annealing durationto which the first zirconium alloy is subjected up to the completion ofthe cladding tube. Preferably, even before the production of thecomposite tube, the second zirconium alloy is subjected to astandardized annealing duration of between 0.1·10⁻¹⁸ h and 3·10⁻¹⁸ h,advantageously at most to a standardized annealing duration of below2·10⁻¹⁸ h.

Preferably, at all events, before the production of the composite tube,a zirconium alloy with 0.8 to 2.8% niobium is treated with a lowerstandardized annealing duration than the zirconium alloy of theprotective layer.

However, a similar method with the same composition and similartreatment of the protective layer (at most a standardized annealingduration of below 3·10⁻¹⁸ h, advantageously below 2·10⁻¹⁸ h) can also beadopted when a zirconium alloy of 1 to 1.8% Sn; 0.2 to 0.6% Fe; up to0.3% Cr (remainder: industrially pure zirconium) is used as matrix,although the matrix should be treated with a standardized annealingduration of 2 to 80·10⁻¹⁸ h before the production of the composite tube.

For the further processing of the composite tube to form the finishedcladding tube, forming steps are necessary (in particular pilgrimsteps), between which intermediate annealing is carried out in eachcase. At the same time, a maximum standardized annealing duration (forexample, 3·10⁻¹⁸ h) is preferably also maintained for this furtherprocessing. Even annealing durations of below 2·10⁻¹⁸ h can easily becontrolled in manufacturing terms.

Insofar as increased protection of the outer surface against uniformcorrosion is desired, during the production of the composite tube athird zirconium alloy may also be bound metallurgically to the firstzirconium alloy.

In accordance with an added feature of the invention, the secondzirconium alloy contains at least 0.2% by weight of iron, a remainderbeing zirconium of industrial purity.

In accordance with an additional feature of the invention, an ironcontent of the second zirconium alloy is 0.40±0.04% by weight.

In accordance with another feature of the invention, the secondzirconium alloy has precipitations of secondary phases, a size of whichcorresponds to a standardized annealing duration of about 0.1 to 3·10⁻¹⁸h.

In accordance with a further feature of the invention, the firstzirconium alloy contains 1.3±0.1% Sn; 0.28±0.04% Fe; 0.16±0.03% Cr;0.01±0.002% Si and 0.14±0.02% O.

In accordance with a further added feature of the invention, the firstzirconium alloy has precipitations of secondary phases, a size of whichcorresponds to a higher standardized annealing duration than anannealing duration to which a size of the precipitations in the secondzirconium alloy corresponds.

In accordance with a further additional feature of the invention, thesize of the precipitations in the first zirconium alloy corresponds to astandardized annealing duration of 2 to 80·10⁻¹⁸ h.

In accordance with another further feature of the invention, the firstzirconium alloy is formed of 0.8 to 2.8% niobium and zirconium ofindustrial purity and also at most 2.7% of further additives.

In accordance with another added feature of the invention, in the firstzirconium alloy, a quantity of the further additives is smaller than aquantity of the niobium.

In accordance with another additional feature of the invention, thefirst zirconium alloy contains 1.0±0.2% niobium, 0.14±0.02% oxygen, aremainder being the zirconium of industrial purity.

In accordance with an added feature of the invention, the firstzirconium alloy contains precipitations of secondary phases, a size ofwhich corresponds to a lower standardized annealing duration, ascompared with the second zirconium alloy.

In accordance with an additional feature of the invention, flow guideblades are provided, and at least the spacers in an upper part of thefuel element carry, on a side facing away from a flow of pressurizedwater, the flow guide blades for intermixing the pressurized water.

In accordance with another feature of the invention, the gastightcladding tubes each have an upper end with a plenum formed therein atthe upper end, and including a gas of an increased pressure filling thegastight cladding tubes.

In accordance with a further feature of the invention, the column offuel pellets have ends and bodies containing virtually no fissionablematerial disposed at the ends.

In accordance with another added feature of the invention, a furtherprotective layer of a third zirconium alloy which is thinner than thematrix and is bonded metallurgically to an outside of the multilayerwall.

In accordance with another additional feature of the invention, thesecond zirconium alloy contains at least 0.30% by weight of iron, aremainder being zirconium of industrial purity. optionally, the secondzirconium alloy contains up to 0.8% by weight of iron, the remainderbeing zirconium of industrial purity. Alternatively, the secondzirconium alloy contains at most 0.6% by weight, of iron, the remainderbeing zirconium of industrial purity.

In accordance with another further feature of the invention, the firstzirconium alloy contains at least 1.2% Sn, at least 0.24% Fe and atleast 0.10% Cr, a remainder being zirconium of industrial purity.Optionally, the first zirconium alloy contains at most 1.5% Sn, at most0.5% Fe and at most 0.25% Cr, a remainder being zirconium of industrialpurity.

In accordance with a concomitant feature of the invention, the size ofthe precipitations in the first zirconium alloy corresponds to astandardized annealing duration of 30±10·10⁻¹⁸ h.

Other features which are considered as characteristic for the inventionare set forth in the appended claims.

Although the invention is illustrated and described herein as embodiedin a fuel element for a pressurized water reactor and a method forproducing cladding tubes, it is nevertheless not intended to be limitedto the details shown, since various modifications and structural changesmay be made therein without departing from the spirit of the inventionand within the scope and range of equivalents of the claims.

The construction and method of operation of the invention, however,together with additional objects and advantages thereof will be bestunderstood from the following description of specific embodiments whenread in connection with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic, side-elevation view of a pressurized waterfuel element according to the invention;

FIG. 2 is a fragmentary, perspective view of guide blades that areadvantageous at least on some spacers or intermediate grids;

FIG. 3 is a graph showing a corrosion rate on the parameter A of thestandardized annealing duration on a surface of a pressurized water fuelrod;

FIGS. 4 and 5 are cut-away, perspective views of a described state of afresh fuel pellet before and after a ramp-like increase in power output;

FIG. 6 is a cross-sectional view of an advantageous interior of a fuelrod;

FIG. 7 is a perspective view of a cladding tube according to the firstpreferred exemplary embodiment;

FIG. 8 is a graph showing phase ranges of the alloys used as a matrix inthe two preferred exemplary embodiments;

FIG. 9 is a flow diagram of method steps for producing the firstexemplary embodiment;

FIG. 10 is a perspective view of the cladding tube according to thesecond preferred exemplary embodiment; and

FIG. 11 is a flow diagram of the method steps for the production of thesecond exemplary embodiment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring now to the figures of the drawing in detail and first,particularly, to FIG. 6 thereof, there is shown a cladding tube 10 ofthe fuel rods 6 is in each case closed in a gastight manner at upper andlower ends by an end plug 11. At the upper end a spring 12 subjected tocompressive stress ensures that a corresponding plenum 13 is maintainedat least at the upper end. A column of fuel pellets 14 contains in eachcase, at its upper and lower end, a body 15 that contains virtually nofissionable material and may consist, for example, of aluminum oxide orelse natural uranium or depleted uranium. In this case, in order toincrease conductivity between the pellets 14 and the cladding tube 10,the cladding tube 10 is filled with a high-pressure gas (for example,helium).

In the present case, a supporting body 16 at the lower end of the fuelrod also keeps free a corresponding plenum.

The outside diameter of the cladding tube is about 9.55 mm, and its wallthickness is about 0.61 mm. According to FIG. 7, a cladding tube 20 isformed of a matrix 21, the thickness of which is about 75 to 95% of acladding tube wall. A protective layer 22 is bound metallurgically tothe matrix 21 on the inside of the cladding tube 20, and it is alsoindicated that a further protective layer 22′ may also be attached tothe outside.

Table 2 indicates the lower and upper limit values for the composition Iof the matrix 21. Here, the values given in brackets in each casedescribe preferred relatively narrow limits for the contents of theindividual alloy constituents or the particularly preferred limit valuesfor the accompanying elements of the alloy constituents which arealready contained as impurities in the zirconium of industrial purity(“sponge”, see Table 1) and can be maintained for the lower limits whichare also advantageous, as in the case of oxygen or silicon.

In the preferred exemplary embodiment, the matrix 21 contains 1.3±0.1%Sn; 0.28±0.04% Fe; 0.16±0.03% Cr; 0.01±0.002% Si and 0.14±0.02% O. Thesize of the precipitated secondary phases is in this case 30·10⁻¹⁸ h.

The protective layer 22 consists of 0.4±0.04% Fe and zirconium sponge,the precipitation size being determined by A=1·10⁻¹⁸ h.

In the second phase, the precipitations consist virtually ofintermetallic ZrFe compounds, in the case of the matrix 21 of mixedcompounds of zirconium with iron and chromium, and, in FIG. 8, it can beseen under I that, up to temperatures of about 820° C., there is anα-phase of ZrSn in addition to the corresponding secondary phase γ ofthese precipitations. In the range between about 820 and 960° C., thereis also a β-phase of ZrSn in addition to the α-phase, and at about 840°C. (“solution temperature”) the γ-phase of the intermetallic compoundsbecomes a solution. Above 960° C., only the β-phase with the dissolvedprecipitations is still stable. If, therefore, the matrix is heated intothe β-range (temperatures of above 960° C.) and is then rapidly cooled,a fine-grained α-phase is first formed, in which part of the iron isdistributed in a finely dispersed manner as precipitations of theγ-phase, while the rest of the iron remains bound as metastablesupersaturation in the α-phase. In this case, the finely dispersedprecipitations correspondingly form nuclei, on which the excess ironfraction is accreted the more rapidly and the more highly, the higherthe temperature and duration in which the matrix material is exposed tofurther thermal treatments in the α-range (temperatures of below 820°C.).

To produce the cladding tube 20, first, the first alloy of ZrSnFeCr,provided for the matrix 21, is remelted a plurality of times under avacuum in a step 30 a (FIG. 9) to homogenize the alloy constituents, ina step 31 a the alloy is forged to a shape suitable for the processingof a tube blank and, in a further step 32 a, the alloy is rapidly cooled(“β-quench”) from a temperature in the β-range (above 960° C.). This maybe followed by further forging (step 33), the first tube blank Ra beingproduced at the latest during a step 34. The step 34 is also followed byfurther annealings, in order to set the parameter A=30·10⁻¹⁸ h in thefirst tube blank.

In a similar way, the second zirconium alloy (ZrFe) provided for theprotective layer 22 is likewise remelted in a step 30 b, in a step 31 bis heated into the β-range (temperatures of above 960° C.) and in thestep 32 b is rapidly cooled. During these steps, a second tube blank Rbis also produced. In this case, the β-quenching (step 32 b) is followedby virtually no further heating, instead the two blanks, the shapes ofwhich have been adapted to one another, are placed one into the other,welded to one another and jointly extruded in a step 35. Thiscoextrusion does not, in practice, contribute to the ripening of theprecipitations, so that, in the composite tube obtained, the matrixmaterial possesses the value A=30·10⁻¹⁸ h and the second zirconium alloypossesses virtually the value A=0. Subsequently, a plurality of pilgrimsteps 36 are carried out, between which brief annealings at temperatureswell below 820° C. are carried out in each case, in order to recover thecold-formed material and prepare it for the next pilgrim step. What isthen achieved by terminal annealing 37 is that the parameter A=1·10⁻¹⁸ his set for the entire processing of the composite tube to form thefinished cladding tube, that is to say the first zirconium alloy of thematrix has the value A=31·10⁻¹⁸ h, but the second zirconium alloy of theprotective layer has the value A=1·10⁻¹⁸ h.

For steps 33 and 34, a range A=2 to 80·10⁻¹⁸ h is maintained, values ofabove 5·10⁻¹⁸ h being advantageous. Values of above 60·10⁻¹⁸ h signifylong annealing durations at high temperatures which do not seemnecessary. For steps 35 to 37, in general, values A of below 2·10⁻¹⁸ maybe maintained. For the finished zirconium alloy of the matrix,therefore, values A=5 to 60·10⁻¹⁸ h seem advantageous, while A=1 to3·10⁻¹⁸ h should be maintained for the second zirconium alloy of theprotective layer.

In the second exemplary embodiment according to FIG. 10, a cladding tube40 is formed of the matrix 41 with the composition 1.0±0.2% Nb,0.14±0.02% O, remainder: zirconium of industrial purity, see Table 2indicating under II the preferred limits for the constituents in similarcompositions.

It can be seen in FIG. 8, under II, that, in the phase diagram of thealloy, at temperatures of up to 580° C. there is a stable α-phase inwhich about half the niobium is dissolved, while the remainder isprecipitated as a stable β-phase of the niobium. At 580° C., there is amixed phase α+β, in which virtually all the niobium is dissolved, while,at temperatures of above 960° C., only a β-phase of the zirconium, withthe completely dissolved niobium, still exists.

The second zirconium alloy in a protective layer 42 of the cladding tube40 is formed of the same ZrFe alloy as in the first preferred exemplaryembodiment already described.

To produce the cladding tube 40, a diagram according to FIG. 11, similarto that of FIG. 9, is obtained. In this case, however, after multipleremelting under a vacuum (step 50 a) and forging in the Orange(temperatures of above 960° C.) (step 51 a), the first zirconium alloyZrNb of the matrix is quenched (step 52), a first tube blank Rc beingproduced from the matrix material, without the β-quenching (step 52 a)being followed by thermal treatment with an appreciable parameter valueA. A step of this kind is provided only for the second zirconium alloyof the protective layer, in which multiple remelting in a vacuum (step50 b) and forging in the β-range (step 51 b) and annealing attemperatures of below about 600° C., in particular below 580° C.(α-range), take place. In this case, the second tube blank Rd isproduced, which is inserted exactly into the interior of the first tubeblank Rc. For the first tube blank Rc produced in steps 51 a and 52 a,virtually the parameter value A=0 is obtained, while, in steps 51 b, 52b and 53, the second tube blank Rd can be produced with a parametervalue below 2·10⁻¹⁸ h. In the exemplary embodiment, A=1·10⁻¹⁸ h was setin step 53.

The two tube blanks inserted one into the other are welded to oneanother and extruded together, subsequently brought to the finaldimensions of the cladding tube (step 55) in a plurality of pilgrimsteps, with recovery annealings interposed between them, and subjectedto terminal annealing 56. In steps 54 to 56, A lower than 0.5·10⁻¹⁸ h ismaintained, even values A lower than 0.1·10⁻¹⁸ h being possible (here:A=0.9·10⁻¹⁸ h).

According to the value A being lower than 0.5·10⁻¹⁸ (preferably, A lowerthan 0.2·10⁻¹⁸, at all events at least lower than 0.3·10⁻¹⁸) for steps50 a to 52 a, in the finished cladding tube preferably a value A lowerthan 0.1·10⁻¹⁸ h is obtained for the first zirconium alloy of the matrix41, whereas a value A=0.1 to 3·10⁻¹⁸ h, preferably between 0.2 and1.5·10⁻¹⁸ h, is obtained for the second zirconium alloy.

The cladding tubes produced in this way are filled with the columns ofrelatively highly enriched fuel pellets and with the high-pressure gas,are closed in a gastight manner by the end plugs and are inserted intothe skeleton mentioned. They have a high burn-up which makes it possibleto have a long period of utilization in the pressurized water reactor.When the pressurized water reactor is in operation, in the control ofthe power output the permissible rates of change need to be coordinatedessentially only with the time constants defined by the physics of thefuel and of the reactor, only minor account needing to be taken ofpossible material damage which, even after lengthy operating times underpart load, could occur on the cladding tubes when the reactor poweroutput is being run up.

TABLE 1 Sponge Zry2 Zyr4 Zr/Nb Composition, Weight % Grades Grades GradeR60802 R60804 Grade Element R60001 R60812 R60814 R60901 Tin . . .1.20-170 1.20-170 . . . Iron . . . 0.07-0.20 0.18-0.24 . . . Chromium .. . 0.05-0.15 0.07-0.13 . . . Nickel . . . 0.03-0.08 . . . . . . Niobium. . . . . . . . . 2.40-2.80 Oxygen {circumflex over ( )} {circumflexover ( )} {circumflex over ( )} 0.09-0.13 Iron + chromium + . . .0.18-0.38 . . . . . . nickel Iron + chromium . . . . . . 0.28-0.37 . . .Maximum Impurities, Weight % Aluminum 0.0075 0.0075 0.0075 0.0075 Boron0.00005 0.00005 0.00005 0.00005 Cadmium 0.00005 0.00005 0.00005 0.00005Carbon 0.027 0.027 0.027 0.027 Chromium 0.020 . . . . . . 0.020 Cobalt0.0020 0.0020 0.0020 0.0020 Copper 0.0050 0.0050 0.0050 0.0050 Hafnium0.010 0.010 0.010 0.010 Hydrogen 0.0025 0.0025 0.0025 0.0025 Iron 0.150. . . . . . 0.150 Magnesium 0.0020 0.0020 0.0020 0.0020 Manganese 0.00500.0050 0.0050 0.0050 Molybdenum 0.0050 0.0050 0.0050 0.0050 Nickel0.0070 . . . 0.0070 0.0070 Nitrogen 0.0080 0.0080 0.0080 0.0080 Silicon0.0120 0.0120 0.0120 0.0120 Tin 0.0050 . . . . . . 0.0050 Tungsten 0.0100.010 0.010 0.010 Uranium (total) 0.00035 0.00035 0.00035 0.00035{circumflex over ( )} When so specified in the purchase order, oxygenshall be determined and reported. Maximum or minimum permissible values,or both, shall be as specified in the purchase order.

TABLE 2 I II Min. Max. Min. Max. Sn 1.0 (1.2)% 1.8 (1.5)% . . . 1.2(0.005) Fe 0.2 (0.24)% 0.6 (0.5/0.4) . . . 1.2 (0.15) Cr (0.8/0.10/0.12)0.3 (0.25/0.20) . . . 0.3 (0.02) Nb . . . . . . 0.8 2.8 (1.3) Remainder:“Zr sponge” with: O (0.10/0.12) (0.20/0.18/0.16) (0.10/0.12)(0.20/0.18/0.16) C . . . (0.01) . . . (0.02) N . . . (0.005) . . .(0.005) Si (0.005/0.007) (0.012) . . . (0.012) P . . . (0.03) . . .(0.03)

1. A fuel element for a pressurized water reactor, comprising: alaterally open skeleton having control-rod guide tubes each with a firstend and a second end, spacers fastened to said control-rod guide tubes,a fuel element head disposed at said first end of said control-rod guidetubes, and a fuel element foot disposed at said second end of saidcontrol-rod guide tubes; and gastight cladding tubes inserted into saidskeleton and each filled with a column of fuel pellets, at least one ofsaid gastight cladding tubes having a multilayer wall, said multilayerwall including: a mechanically stable matrix formed of a first zirconiumalloy disposed in a middle of said multilayer wall, said first zirconiumalloy containing 1.0 to 1.8% Sn, 0.2 to 0.6% Fe, and up to 0.3% Cr, aremainder being zirconium of industry purity, said first zirconium alloyhaving precipitations of secondary phases, a size of the precipitationscorresponding to a standardized annealing duration of 2 to 80×10^(−˜)h;and a thinner protective layer of a second zirconium alloy alloyed to alesser extent than said first zirconium alloy, said thinner protectivelayer bound metallurgically to said matrix and disposed on an inside ofsaid matrix facing said fuel pellets, said second zirconium alloycontaining at least 0.2% and up to 0.8% by weight of iron, a remainderbeing zirconium of industrial purity, said second zirconium alloy havingprecipitations of secondary phases, a size of the precipitationscorresponding to a standardized annealing duration of about 0.1 to3×10⁻¹⁸ h.
 2. The fuel element according to claim 1, wherein an ironcontent of said second zirconium alloy is 0.40±0.04% by weight.
 3. Thefuel element according to claim 1, wherein said first zirconium alloycontains 1.3±0.1% Sn; 0.28±0.04% Fe; 0.16±0.03% Cr; 0.01±0.002% Si and0.14±0.02% O.
 4. The fuel element according to claim 1, including flowguide blades being carried by at least said spacers in an upper part ofsaid fuel element, on a side facing away from a flow of pressurizedwater, for intermixing the pressurized water.
 5. The fuel elementaccording to claim 1, including a further protective layer of a thirdzirconium alloy which is thinner than said matrix and is bondedmetallurgically to an outside of said multilayer wall.
 6. The fuelelement according to claim 1, wherein said second zirconium alloycontains at least 0.30% by weight of iron, a remainder being zirconiumof industrial purity.
 7. The fuel element according to claim 1, whereinsaid second zirconium alloy contains at most 0.6% by weight, of iron, aremainder being zirconium of industrial purity.
 8. The fuel elementaccording to claim 1, wherein said first zirconium alloy contains atleast 1.2% Sn, at least 0.24% Fe and at least 0.10% Cr, a remainderbeing zirconium of industrial purity.
 9. The fuel element according toclaim 1, wherein said first zirconium alloy contains at most 1.5% Sn, atmost 0.5% Fe and at most 0.25% Cr, a remainder being zirconium ofindustrial purity.
 10. The fuel element according to claim 1, whereinthe size of the precipitations in said first zirconium alloy correspondsto a standardized annealing duration of 30±10·10⁻¹⁸ h.
 11. A method forproducing a cladding tube for a fuel rod of a pressurized water reactor,which comprises the steps of: providing a first zirconium alloycontaining 1.0 to 1.8% Sn, 0.2 to 0.6% Fe, and up to 0.3% Cr, aremainder being zirconium of industry purity; providing a secondzirconium alloy containing at least 0.2% and up to 0.8% by weight ofiron, a remainder being zirconium of industrial purity; thermallytreating the first zirconium alloy and the second zirconium alloydifferently and independent of one another, in each case solutionannealing, with subsequent-different standardized annealing durations of2 to 80×10⁻¹⁸ h and 0.1 to 3×10⁻¹⁸ h, respectively; producing from thefirst zirconium alloy and at least the second zirconium alloy amultilayer composite tube, a wall of the multilayer composite tubecontaining, in a middle region, as a matrix, a thick layer of the firstzirconium alloy, and to an inside of the thick layer of the firstzirconium alloy a protective layer formed of the second zirconium alloy,the protective layer being bonded to the matrix metallurgically; andprocessing the multilayer composite tube further into a finishedcladding tube, in such a way that the protective layer and the thicklayer are subjected to substantial equivalent thermal conditions,without the solution annealing.
 12. The method according to claim 11,which comprises forming the second zirconium alloy to contain 0.2 to0.5% by weight of iron, a remainder being zirconium of industrialpurity, and, before the production of the multilayer composite tube, thesecond zirconium alloy is treated at most with a standardized annealingduration of below 2×10⁻¹⁸ h.
 13. The method according to claim 11 whichcomprises forming the second zirconium alloy to contain 0.4±0.04% byweight of iron.
 14. The method according to claim 11, which comprisesfurther processing the multilayer composite tube into the finishedcladding tube with a standardized annealing duration of below 3×10⁻¹⁸ h.15. The method according to claim 11, which comprises during theproduction of the multilayer composite tube, a third zirconium alloy isbonded metallurgically to the first zirconium alloy.
 16. The methodaccording to claim 11, which comprises subjecting the second zirconiumalloy to a standardized annealing duration of about 1±0.5×10⁻¹⁸ h beforea production of the multilayer composite tube.
 17. The method accordingto claim 11, which comprises forming the second zirconium alloy tocontain 0.3 to 0.5% by weight of iron, a remainder being zirconium ofindustrial purity, and, before the production of the multilayercomposite tube, the second zirconium alloy is treated at most with astandardized annealing duration of below 2×10⁻¹⁸ h.
 18. The methodaccording to claim 11, which comprises further processing the multilayercomposite tube into the finished cladding tube with a standardizedannealing duration of below 2×10⁻¹⁸ h.
 19. A cladding tube for a fuelrod of a pressurized water reactor, in combination with a column of fuelpellets filled therein, comprising: a multilayer wall, including: amechanically stable matrix formed of a first zirconium alloy disposed ina middle of said multilayer wall, said first zirconium alloy containing1.0 to 1.8% Sn, 0.2 to 0.6% Fe, and up to 0.3% Cr, a remainder beingzirconium of industry purity, said first zirconium alloy havingprecipitations of secondary phases, a size of the precipitationscorresponding to a standardized annealing duration of 2 to 80×10⁻¹⁸ h;and a thinner protective layer of a second zirconium alloy alloyed to alesser extent than said first zirconium alloy, said thinner protectivelayer bound metallurgically to said matrix and disposed on an inside ofsaid matrix facing said fuel pellets, said second zirconium alloycontaining at least 0.2% and up to 0.8% by weight of iron, a remainderbeing zirconium of industrial purity, said second zirconium alloy havingprecipitations of secondary phases, a size of the precipitationscorresponding to a standardized annealing duration of about 0.1 to3×10⁻¹⁸ h.